New synthetic method for functionally substituted morpholinium 1,4-dihydropyridine-2-thiolates and their derivatives

Article abstract of DOI:10.1134/S1070428007020194

By condensation of aromatic aldehydes with cyanothioacetamide and enamines of 1,3-dicarbonyl compounds functionally substituted morpholinium 1,4-dihydropyridine-2-thiolates were obtained applied to the synthesis of 2-alkylsulfanyl-1,4-dihydropyridines, 1,4-dihydrothieno[2,3-b]-pyridines, and 2,3,4,7-tetrahydrothiazolo[3,2-a]pyridine.

Full text of DOI:10.1134/S1070428007020194

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 2, pp. 271−275. © Pleiades Publishing, Ltd. 2007.
Original Russian Text © V.D. Dyachenko, 2007, published in Zhurnal Organicheskoi Khimii, 2007, Vol. 43, No. 2, pp. 278−282.
New Synthetic Method for Functionally Substituted Morpholinium
1,4-Dihydropyridine-2-thiolates and Their Derivatives
V. D. Dyachenko
Taras Shevchenko National Pedagogical University, Lugansk, 91011 Ukraine
e-mail: dvd_lug@online.lg.ua
Received November 26, 2005
Abstract—By condensation of aromatic aldehydes with cyanothioacetamide and enamines of 1,3-dicarbonyl
compounds functionally substituted morpholinium 1,4-dihydropyridine-2-thiolates were obtained applied to the
synthesis of 2-alkylsulfanyl-1,4-dihydropyridines, 1,4-dihydrothieno[2,3-b]-pyridines, and 2,3,4,7-tetra-
hydrothiazolo[3,2-a]pyridine.
DOI: 10.1134/S1070428007020194
Interest in functionalized ammonium 1,4-dihydro-
pyridine-2-thiolates is due to opportunities of preparing
therefrom biologically active compounds with antioxidant
[1], hepatoprotector [2], and cardiovascular [3] qualities.
The following methods of synthesis for this class com-
pounds were developed: three-component condensation
of aldehydes, cyanothioacetamide, and 1,3-dicarbonyl
compounds [4], reaction of aryl(heteryl)methylenecyano-
thioacetamide with 1,3-dicarbonyl compounds [5], and
reaction of substituted ethyl acrylates with cyanothio-
acetamide [6].
The structure of salts Ia–Ic was confirmed by spectral
findings. In the IR spectra characteristic absorption bands
were observed of the stretching vibrations of a conjugated
cyano group and a carbonyl group at 2180–2194 and
1684–1695 cm–1 respectively. 1H NMR spectra of com-
pounds Ia–Ic alongside the characteristic signals of the
substituents and of the morpholinium cation contained
proton signals from the 1,4-dihydropyridine ring as singlets
at δ 4.21–4.42 (C4H) and 8.01–8.31 (N1H) ppm in
agreement with the data of [7, 9].
Involving in this condensation 4-butoxybenzaldehyde
(IId) resulted in the formation of 5-acetyl-4-(4-butoxy-
phenyl)-6-methyl-2-thioxo-1,2,3,4-tetrahydropyridine-3-
carbonitrile (V) existing in DMSO solution as a mixture
of nearly equal amounts of thionethiol prototropic tauto-
mers VA and VB as showed 1H NMR spectra. The direc-
tion of the chemical transformation of salts Ia–Ic and
thione V also confirms their structure. In particular, the
boiling in ethanol of compound Ia results in the aromatiza-
tion of the 1,4-dihydropyridine ring, apparently by air oxy-
gen, and in the formation of morpholinium 6-methyl-4-(4-
chlorophenyl)-3-cyano-5-ethoxycarbonylpyridine-2-thio-
late (VI).Alkylation of salts Ib and Ic in DMF with com-
pounds VIIa and VIIb gives the corresponding thioethers
VIIIa and VIIIb. At the same time the alkylation of salt
Ic with 1,2-dibromoethane did not stop at the formation
of the corresponding thioether C, but an intramolecular
alkylation of a nitrogen from the dihydropyridine ring with
the bromoethyl moiety occurred providing allyl-5-methyl-
In extension of our studies on the chemistry of partially
hydrogenated pyridine-2-chalcogenones [7] we developed
a new synthetic procedure for morpholinium 4-aryl-
(heteryl)-6-methyl-3-cyano-1,4-dihydropyridine-2-thio-
lates Ia–Ic involving a three-component condensation of
aromatic aldehydes IIa–IId, cyanothioacetamide (III),
and enamines of 1,3-dicarbonyl compounds IVa–IVc in
ethanol at 20°C in the presence of morpholine. The reac-
tion pathway is likely to start with the formation of
aryl(heteryl)methylenecyanothioacetamides A resulting
from condensation of aldehydes IIa–IId with cyanothio-
acetamide (III) by Knoevenagel reaction. Then follows
the alkylation of alkenes A with enamines of 1,3-dicarbonyl
compounds IVa–IVc by Stork reaction type [8].Adducts
B thus formed undergo an intramolecular transamination
that finishes in heterocyclization into substituted morpho-
linium 4-aryl-(heteryl)-6-methyl-3-cyano-1,4-dihydropyri-
dine-2-thiolates Ia–Ic.
271

DYACHENKO
272
Y
R
CN
O
CN
S
RCHO
+
+
_
H2O
IV
_
N
O
S
NH2
IIа IId
H2N
Me
III
_
A
IVа IVc
Cl
OBu
R
O
Y
CN
O
EtO
O
CN
S_
CN
S
H2N
S
Me
N
Me
+
O
H2N
O
Me
N
Me
N
H
B
VI
VA
_
2[H]
OBu
NHZ
Cl
O
R
O
R
O
CN
CN
S
Y
VIIа, VIIb
Y
O
S_
NHZ
Br
+
Me
N
H
Me
N
H
CN
SH
H2N
O
Me
O
O
_
Me
N
H
VIIIа, VIIIb
Iа Ic
Br
VC
Br
Cl
Y
CN
Cl
CN
OBu
O
O
O
R
CN
S
CN
O
CN
S
Me
N
H
Me
N
H
S
CN
Me
Me
N
H
E
Br
D
C
OBu
O
O
O
O
R
NH2
O
CN
Y
CN
S
CN
Me
S
Me
N
S
Me
N
H
Me
N
H
XI
Xа, Xb
IX
I, R = 4-ClC6H4, Y = EtO (a), R = 4-HOC6H4, Y = Me (b), R = 2-furyl, Y = CH2=CHCH2O (c); II, R = 4-ClC6H4 (a), 4-HOC6H4 (b),
2-furyl (c), 4-BuOC6H4 (d); IV,Y= EtO (a), Me (b), CH2=CHCH2O (c); VII, Z = H (a), 2-thiazolyl (b); VIII, R = 4-HOC6H4,Y=
Me, Z = H (a), R = 2-furyl, Y = CH2=CHCH2O, Z = 2-thiazolyl (b); X, R = 2-furyl, Y = CH2=CHCH2O (a), R = 4-BuOC6H4, Y =
Me (b).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 2 2007

NEW SYNTHETIC METHOD FOR FUNCTIONALLY SUBSTITUTED MORPHOLINIUM
273
7-(2-furyl)-8-cyano-2,3,4,7-tetrahydrothiazolo[3,2-
a]pyridine-6-carboxylate (IX). A reaction of salt Ic and
thione V with α-chloroacetonitrile in DMF led to the
formation of substituted 4,7-dihydrothieno[2,3-b]pyridines
Xa and Xb resulting from the intramolecular dimerization
of D by Thorpe–Ziegler reaction [10]. Alkylation of
mercaptan V with allyl bromide in DMF did not finish at
the formation of the corresponding thioether E due to the
ready trans-formation of the latter under the reaction
conditions into 3-allyl-5-acetyl-4-(4-butoxyphenyl)-6-
methyl-2-oxo-1,2,3,4-tetrahydropyridine-3-carbonitrile
(XI) originating from the regioselective [3,3]-sigmatropic
rearrangement characteristic of the substituted 2-
allylsulfanyl-1,4-di-hydropyridine systems [11].
thiolate (Ia). To a mixture of 1.4 g (10 mmol) of 4-chloro-
benzaldehyde (IIa) and 1.0 g (10 mmol) of cyano-
thioacetamide (III) in 15 ml of ethanol was added at
20°C 2 drops of morpholine, and the mixture was stirred
for 10 min. Therewith the initial compounds dissolved,and
alkene A formed. Then 1.99 g (10 mmol) of ethyl aceto-
acetate enamine (IVa) was added, and the reaction
mixture was stirred for 1h and left standing for 24 h.
Then the precipitate formed was filtered off, washed with
ethanol and hexane. Yield 2.70 g (64%), yellow powder,
mp 147–149°C. IR spectrum, cm–1: 2194 (C≡N), 1692
(C=O). 1H NMR spectrum, δ, ppm: 1.10 t (3H, MeCH2,
J 7.04 Hz), 2.55 s (3H, Me), 3.07 t (4H, CH2NCH2,
J 4.78 Hz), 3.75 t (4H, CH2OCH2), 3.93 q (2H, CH2),
4.32 s (1H, C4H), 7.10 d and 7.16 d (2H each, C6H4,
J 8.42 Hz), 8.01 br.s (1H, NH). Found, %: C 56.80;
H 5.61; N 9.79. C20H24ClN3O3S. Calculated, %: C 56.93;
H 5.73; N 9.96.
The spectral characteristics of compounds V, VI,
VIIIa, VIIIb, and IX–XI confirm their structure. The
1
special feature of the H NMR spectra of thioethers
VIIIa and VIIIb consists in the nonequivalence of the
protons in the SCH2 group giving rise to appearance of
Morpholinium 5-acetyl-4-(4-hydroxyphenyl)-6-
methyl-3-cyano-1,4-dihydropyridine-2-thiolate (Ib)
was obtained similarly from 4-hydroxybenzaldehyde (IIb)
and acetylacetone enamine (IVb). Yield 2.65 g (71%),
colorless powder, mp 144–146°C. IR spectrum, cm–1:
3595 (OH), 2188 (C≡N), 1684 (C=O). 1H NMR spectrum,
δ, ppm: 1.92 C (3H, MeCO), 2.23 C (3H, Me), 3.06 t
(4H, CH2NCH2, J4.73 Hz), 3.74 t (4H, CH2OCH2),
4.21 s (1H, C4H), 6.63 d and 6.90 d (2H each, C6H4,
J 8.53 Hz), 8.18 br.s (1H, NH), 10.11 br.s (1H, OH).
Found, %: C 60.89; H 6.02; N 11.04. C19H23N3O3S.
Calculated, %: C 61.10; H.21; N 11.25.
2
the signals as two doublets with a coupling constant J.
This fact may be understood assuming the lack of free
rotation of the alkylsulfanyl moiety around the ordinary
bonds originating likely from the existence of a an intra-
molecular hydrogen bond between the H1 atom of the
dihydropyridine ring and the oxygen of the amide fragment.
The presence of such a bond in the molecules of the
1,4-dihydropyridine systems can increase their stability
against aromatization [12].
EXPERIMENTAL
Morpholinium 5-allyloxycarbonyl-6-methyl-4-(2-
furyl)-3-cyano-1,4-dihydropyridine-2-thiolate (Ic)
was obtained similarly to salt Ia from furfural and
enamine IVc. Yield 3.46 g (89%), red powder, mp 178–
180°C (sublim. at 150°C). IR spectrum, cm–1: 2180
(C≡N), 1695 (C=O). 1H NMR spectrum, δ, ppm: 2.20 C
(3H, Me), 3.08 t (4H, CH2NCH2, J4.69 Hz), 3.74 t (4H,
CH2OCH2), 4.42 s (1H, C4H), 4.48 d (2H, CH2O,
J 6.41 Hz), 5.03 d (1H, CH2=, Jtrans 9.44 Hz), 5.17 d (1H,
CH2=, Jcis 9.45 Hz), 5.78 d (1H, C3H of furan,
J 2.99 Hz), 5.81 m (1H, =CH), 6.23 d.d (1H, C4H of
furan, J 2.38 Hz), 7.40 d (1H, C5H of furan, J 1.20 Hz),
8.31 br.s (1H, NH). Found, %: C 58.40; H.78; N 10.66.
C19H23N3O4S. Calculated, %: C 58.59; H.95; N 10.79.
IR spectra were recorded on a spectrophotometer
IKS-40 from mulls in mineral oil. H NMR spectra
1
were registered on spectrometers Bruker WP-100SY
(100 MHz) (compounds Ib, Ic, VIIIa, Xb) Gemini-200
(199.975 MHz) (compound Ia), Bruker AM-300
(300.13 MHz) (compound VI), Varian Mercury-400
(400.397 MHz) (compounds VIIIb, XI), and Bruker DRX
500 (500.13 MHz) (compounds IX, Xa) from solutions
in DMSO-d6 with TMS as an internal reference. Mass
spectrum of compound VIIIb was measured on Chrom-
mas GC/MS-Hewlett-Packard 5890/5972 instrument,
column HP-5MS (70 eV) in CH2Cl2 solution. Melting
points were determined on a Koeffler heating block. The
reactions progress was monitored and the purity of
compounds obtained was checked by TLC on Silufol UV-
254 plates, eluent acetone–hexane, 3:5, development in
iodine vapor or under UV irradiation.
5-Acetyl-4-(4-butoxyphenyl)-6-methyl-2-thioxo-
1,2,3,4-tetrahydropyridine-3-carbonitrile (V) was
obtained similarly from 4-butoxybenzaldehyde and
enamine IVb. Yield 2.33 g (68%), yellow powder, mp
172–174°C (EtOH). IR spectrum, cm–1: 2248 (C≡N),
Morpholinium 6-methyl-4-(4-chlorophenyl)-3-
cyano-5-ethoxycarbonyl-1,4-dihydropyridine-2-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 2 2007

DYACHENKO
274
1
1684 (C=O). H NMR spectrum, δ, ppm: 0.92 t (3H,
MeCH2, J 6.11 Hz), 1.14–1.79 m (4H, 2CH2), 2.03 s
(3H, MeCO), 2.33 s (3H, Me), 3.93 t (2H, OCH2,
J 5.99Hz), 4.31 d (0.5H, C3H, J4.13 Hz), 4.46 s and
4.95 d (1H, C4H), 6.86 d and 7.07 d (2H each, C6H4,
J 8.51 Hz), 11.99 br.s and 12.19 br.s (1H, NH). Found,
%: C 66.49; H.32; N 8.14. C19H22N2O2S. Calculated,
%: C 66.64; H.48; N 8.18.
(1H, C5H of furan, J1.21 Hz), 7.44 d (1H, C4H of
thiazole), 9.72 br.s (1H, NH), 12.43 br.s (1H, CONH).
Mass spectrum, m/z (Irel, %): 443 (100)[M + 1]+, 440
(39)[M – 2]+, 375 (28), 343 (15), 275 (22), 101 (14).
Found, %: C 54.10; H.95; N 12.48. C20H18N4O4S2.
Calculated, %: C.28; H.10; N 12.66. M 442.51.
Allyl 5-methyl-7-(2-furyl)-8-cyano-2,3,4,7-
tetrahydrothiazolo[3,2-a]pyridine-6-carboxylate (IX)
was obtained similarly from salt Ic and 1,2-dibromo-
ethane. Yield 2.75 g (84%), dark red crystals, mp 105°C
(MeOH). IR spectrum, cm–1: 2200 (C≡N), 1688 (C=O).
1H NMR spectrum, δ, ppm: 2.45 s (3H, Me), 3.41 m
(2H, NCH2), 4.19m (2H, SCH2), 4.54 m (2H, OCH2),
4.76 s (1H, C7H), 5.15 d (1H, CH2=, Jcis 9.31 Hz), 5.24 d
(1H, CH2=, Jtrans 17.48 Hz), 5.86 m (1H, =CH), 6.06 d
(1H, C3H of furan, J2.81 Hz), 6.37 d.d (1H, C4H of furan,
J2.35 Hz), 7.51 d (1H, C5H of furan, J1.18 Hz). Found,
%: C 61.98; H.78; N.42. C17H16N2O3S. Calculated, %:
C.18; H.91; N 8.53. M 328.39.
Morpholinium 6-methyl-4-(4-chlorophenyl)-3-
cyano-5-ethoxycarbonylpyridine-2-thiolate (VI). A
suspension of 4.22 g (10 mmol) of salt Ia in 15 ml of
ethanol was boiled for 2 h, on cooling the precipitate was
filtered off and washed with acetone. Yield 3.44 g (82%),
yellow crystals, mp 210–212°C (sublim. at 150°C). IR
spectrum, cm–1: 2212 (C≡N), 1726 (C=O). H NMR
1
spectrum, δ, ppm: 0.80 t (3H, MeCH2, J 6.90 Hz), 2.35 s
(3H, Me), 3.11 t (4H, CH2NCH2, J4.80 Hz), 3.76 t (4H,
CH2OCH2), 3.86 q (2H, MeCH2), 7.27 d and 7.53 d (2H
each, C6H4, J 8.70 Hz). Found, %: C 57.02; H.12; N
9.85. C20H22ClN3O3S. Calculated, %: C 57.21; H.28; N
10.00.
Allyl 3-amino-6-methyl-4-(2-furyl)-2-cyano-4,7-
dihydrothieno[2,3-b]pyridine-5-carboxylate (Xa) was
obtained similarly from salt Ic and α-chloroacetonitrile.
Yield 2.35 g (69%), yellow powder, mp 204–207°C
(1-BuOH), fluorescent under UV irradiation. IR spec-
trum, cm–1: 3295–3442 (NH2), 2194 (C≡N), 1688 (C=O),
1647 [δ(NH2)]. 1H NMR spectrum, δ, ppm: 2.29 s (3H,
Me), 4.51 m (2H, OCH2), 5.11 d (1H, CH2=, Jcis 9.37 Hz),
5.20 d.d (1H, C4H), 5.25 d (1H, CH2=, Jtrans 17.42 Hz),
5.79 m (1H, =CH), 6.03 br.s (2H, NH2), 6.09 d (1H, C3H
of furan, J2.81 Hz), 6.22 d.d (1H, C4H of furan,
J 2.38 Hz), 7.34 d (1H, C5H of furan, J1.24 Hz), 9.86 br.s
(1H, NH). Found, %: C 59.70; H.35; N.18. C17H15N3O3S.
Calculated, %: C.81; H.43; N 12.31.
5-Acetyl-4-(4-hydroxyphenyl)-2-carbamoyl-
ethylsulfanyl-1,4-dihydropyridine-3-carbonitrile
(VIIIa). To a suspension of 3.73 g (10 mmol) of salt Ib in
15 ml of DMF was added 0.94 g (10 mmol) of α-chloro-
acetamide, the mixture was stirred for 3 h and diluted
with an equal volume of water. After 24 h the precipitate
was filtered off and washed with water, ethanol, and
hexane. Yield 2.44 g (71%), yellow powder, mp 189–
191°C (PrOH). IR spectrum, cm–1: 3300 (NH), 2192
(C≡N), 1690 (C=O). 1H NMR spectrum, δ, ppm: 2.03 s
(3H, MeCO), 2.28 s (3H, Me), 3.55 d and 3.81 d (1H,
SCH2, 2J 14.13 Hz), 4.51 s (1H, C4H), 6.70 d and 6.99 d
(2H each, C6H4, J 7.99 Hz), 7.50 br.s and 7.88 br.s (1H
each, NH2), 9.30 br.C (1H, NH), 10.25br.s (1H, OH).
Found, %: C 59.33; H.78; N 12.07. C17H17N3O3S.
Calculated, %: C.46; H.99; N 12.24.
3-Amino-5-acetyl-4-(4-butoxyphenyl)-6-methyl-
4,7-dihydrothieno[2,3-b]pyridine-2-carbonitrile
(Xb). To a stirred solution of 3.42 g (10 mmol) of
pyridinethiol V in 15 ml of DMF was added in succession
5.6 ml (10 mmol) of 10% water solution of KOH and
0.63 ml (10 mmol)of α-chloroacetonitrile, the mixture was
stirred for 3 h, diluted with equal volume of water, and
left standing for 24 h. The precipitate was filtered off,
washed with water, ethanol, and hexane. Yield 2.74 g
(72%), yellow crystals, mp 205–207°C (AcOH–EtOH,
1:1). IR spectrum, cm–1: 3285–3449 (NH2), 2204 (C≡N),
1687 (C=O), 1649 [δ(NH2)]. 1H NMR spectrum, δ, ppm:
0.89 t (3H, MeCH2, J 7.12 Hz), 1.15–1.87 m (4H, 2CH2),
2.08 s (3H, MeCO), 2.28 s (3H, Me), 3.86 t (2H, OCH2,
J7.08 Hz), 5.07 s (1H, C4H), 6.28 br.s (2H, NH2), 6.77 d
and 7.22 d (2H each, C6H4, J 8.55 Hz), 9.88 br.s (1H,
Allyl 6-methyl-2-(thiazol-2-ylcarbamoylmethyl-
sulfanyl)-4-(2-furyl)-3-cyano-1,4-dihydropyridine-5-
carboxylate (VIIIb) was obtained in the same way as
thioether VIIIa from salt Ic and compound VIIb. Yield
3.49 g (79%), colorless powder, mp 209–210°C (1-BuOH).
IR spectrum, cm–1: 3312 (NH), 2198 (C≡N), 1693 (C=O).
1H NMR spectrum, δ, ppm: 2.38 s (3H, Me), 3.84 d and
3.96 d (ïO 1H, SCH2, 2J 13.98 Hz), 4.52 m (2H, CH2O),
4.71 s (1H, C4H), 5.10 d (1H, CH2=, Jcis 9.49 Hz), 5.18 d
(1H, CH2=, Jtrans 17.33 Hz), 5.84 m (1H, =CH), 6.00 d
(1H, C3H of furan, J2.88 Hz), 6.21 d.d (1H, C4H of furan,
J2.41 Hz), 7.05 d (1H, C5H of thiazole, J3.01Hz), 7.32 d
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 2 2007

NEW SYNTHETIC METHOD FOR FUNCTIONALLY SUBSTITUTED MORPHOLINIUM
p. 239.
275
NH). Found, %: C 65.91; H.89; N.84. C21H23N3O2S.
5. Sharanin, Yu.A., Shestopalov, A.M., Rodinovskaya, L.A.,
Nesterov, V.N., Shklover, V.E., Struchkov, Yu.T.,
Promonenkov, V.K., and Litvinov, V.P., Zh. Org. Khim., 1986,
vol. 22, p. 2600; Krauze, A. and Duburs, G., Latv. Kim. Z.,
1994, p. 928; Dyachenko, V.D., Krivokolysko, S.G., and
Litvinov, V.P., Zh. Org. Khim., 1998, vol. 34, p. 927.
6. Rubio, M.J., Seoane, C., Soto, J.L., and Susaeta, A. Lieb.
Ann., 1986, 210; Krauze,A.A., Liepin’sh, E.E., Pelcher,Yu.E.,
Kalme, Z.A., Dipan, I.V., and Dubur, G.Ya., Khim.
Geterotsikl. Soedin., 1985, p. 95.
7. Dyachenko, V.D., Krivokolysko, S.G., and Litvinov, V.P.,
Khim. Geterotsikl. Soedin., 1997, p. 666; Dyachenko, V.D.,
Nikishin, A.A., and Litvinov, V.P., Khim. Geterotsikl.
Soedin., 1997, p. 996; Dyachenko, V.D., Krivokolysko, S.G.,
and Litvinov, V.P., Izv. Akad. Nauk, Ser. Khim., 1997,
p. 2016; Dyachenko, V.D., Litvinov, V.P., Zh. Org. Khim.,
1998, vol. 34, p. 589.
Calculated, %: C.12; H.08; N 11.01.
3-Allyl-5-acetyl-4-(4-butoxyphenyl)-6-methyl-2-
thioxo-1,2,3,4-tetrahydropyridine-3-carbonitrile
(XI) was obtained similarly from allyl bromide. Yield
2.60 g (68%), yellow powder, mp 151–153°C (EtOH).
IR spectrum, cm–1: 2255 (C≡N), 1679 (C=O). 1H NMR
spectrum, δ, ppm: 0.98 t (3H, MeCH2, J 7.09 Hz),
1.48 m (2H, CH2), 1.73 m (2H, CH2), 2.00 s (3H,
MeCO), 2.36 s (3H, Me), 2.61 m (2H, CH2CH=),
3.91 m (3H, C4H and SCH2), 5.19 d (1H, CH2=,
Jtrans 17.45 Hz), 5.36 d (1H, CH2=, Jcis 9.16 Hz), 5.97 m
(1H, =CH), 6.79 d and 7.08 d (2H each, C6H4,
J 8.49 Hz), 11.94 br.C (1H, NH). Found, %: C 68.92;
H.74; N.19. C22H26N2O2S. Calculated, %: C.08; H.85;
N 7.32.
8. Stork, G., Brizzolara,A., Landesman, H., Szmuszkovicz, J.,
and Terrell, R., J. Am. Chem. Soc., 1963, vol. 85, p. 207;
Stork, G. and Landesman, H.K., J. Am. Chem. Soc., 1956,
vol. 78, p. 5128.
9. Sharanin, Yu.A., Krivokolysko, S.G., and Dyachenko, V.D.,
Zh. Org. Khim., 1994, vol. 30, p. 581.
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